JP2017160303A - Bisphenol resin powder, electrode, lead storage battery and method of producing the same, and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bisphenol resin powder which makes it possible to obtain excellent cycle characteristics in a lead storage battery.SOLUTION: A bisphenol resin powder is obtained by the reaction among (a) a bisphenol compound, (b) at least one selected from the group consisting of aminonaphthalenesulfonic acid and aminonaphthalenesulfonic acid derivatives, and (c) at least one selected from the group consisting of formaldehyde and formaldehyde derivatives.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a bisphenol-based resin powder, an electrode, a lead storage battery, a production method thereof, and a resin composition.

  BACKGROUND ART Lead-acid batteries for automobiles are widely used for engine starting and power supply for electrical components. In recent years, an idling stop system (hereinafter referred to as “ISS”) that stops the engine when the vehicle is temporarily stopped and restarts when the vehicle starts is being implemented as an effort to protect the environment and improve fuel efficiency. In the lead storage battery used in ISS, the engine is frequently started and stopped repeatedly, so that the number of large current discharges at the start of the engine increases, and the use of electrical components overlaps with the discharge load.

Charging of the lead acid battery for automobiles is constant voltage charging by an alternator. In recent years, the set value of the alternator voltage has been lowered for the purpose of suppressing a decrease in the electrolyte due to water decomposition during charging. Further, in recent years, in addition to adopting such a low charging voltage, a power generation control system called “charging by an alternator during traveling is controlled according to the traveling state of the vehicle and the charged state of the lead storage battery. The system that reduces engine load, improves fuel consumption, and reduces CO ₂ is also employed. In such a system, it is difficult to charge the lead storage battery, and it is difficult to achieve a fully charged state. Under such conditions of use, lead-acid batteries are often not fully charged and used due to excessive discharge.

  If the lead storage battery is not fully charged and the state of low charge continues, a phenomenon (sulfation) in which lead sulfate as an inactive discharge product accumulates on the electrode plate may occur. In such a situation, it is known that battery performance such as cycle characteristics deteriorates because the active material is difficult to be reduced (it is difficult to be charged).

  Moreover, when it is difficult to perform complete charging, a stratification phenomenon occurs in which a difference in concentration of dilute sulfuric acid, which is an electrolytic solution, occurs between the upper and lower portions of the electrode plate in the lead acid battery. In this case, the concentration of dilute sulfuric acid in the lower part of the electrode plate increases and sulfation occurs. For this reason, the reactivity of the lower part of the electrode plate is reduced, and only the upper part of the electrode plate reacts intensively. As a result, deterioration such as weakening of the connection between the active materials progresses, and the active material peels off from the current collector supporting the active material (for example, current collector grid) at the upper part of the electrode plate, so that the battery having cycle characteristics and the like Performance decreases.

  On the other hand, as a means for improving cycle characteristics and the like, the following Patent Document 1 discloses a technique relating to a negative electrode for a lead storage battery obtained by using a negative electrode active material and a condensate of phenols, aminobenzenesulfonic acid and formaldehyde. It is disclosed.

International Publication No. 1997/37393 JP2015-137330A

  By the way, in order to further improve battery performance such as charge / discharge characteristics and cycle characteristics of the lead storage battery, it is required to improve the storage stability of the resin for fixing the electrode active material.

  This invention is made | formed in view of the said situation, and it aims at providing the bisphenol-type resin powder which can obtain the battery performance outstanding in the lead acid battery, and its manufacturing method. Another object of the present invention is to provide a resin composition containing the bisphenol-based resin powder. Furthermore, an object of this invention is to provide the electrode and lead acid battery which are manufactured using an electrode active material and the said bisphenol-type resin powder, and these manufacturing methods.

  As a result of the study by the present inventors, it has been clarified that sufficient charging characteristics cannot be obtained when the negative electrode for a lead storage battery described in Patent Document 1 is used. In contrast, the present inventors react a bisphenol compound with at least one selected from the group consisting of aminonaphthalenesulfonic acid and aminonaphthalenesulfonic acid derivatives and at least one selected from the group consisting of formaldehyde and formaldehyde derivatives. It has been found that the charging characteristics are improved by using a bisphenol-based resin obtained by the method (Patent Document 2). However, even in the invention described in Patent Document 2, it has become clear that the charging characteristics and the discharging characteristics are in a trade-off relationship, and it is necessary to achieve both characteristics. As a result of intensive studies by the present inventors, a bisphenol compound is reacted with at least one selected from the group consisting of aminobenzenesulfonic acid and aminobenzenesulfonic acid derivatives and at least one selected from the group consisting of formaldehyde and formaldehyde derivatives. It is found that the above problem can be solved by applying a powder having an average particle diameter defined in the bisphenol-based resin obtained and using a mixture of bisphenol A and bisphenol S as the bisphenol-based compound contained in the powder. It was.

  That is, the bisphenol-based resin powder according to the present invention includes (a) a bisphenol-based compound, (b) at least one selected from the group consisting of aminonaphthalenesulfonic acid and aminonaphthalenesulfonic acid derivatives, and (c) formaldehyde and formaldehyde derivatives. It is obtained by reacting at least one selected from the group consisting of

  Moreover, it is preferable that the average particle diameter of the bisphenol-type resin powder which concerns on this invention is 10-250 micrometers.

  According to the bisphenol-based resin powder according to the present invention, excellent charge / discharge characteristics can be obtained in a lead storage battery. Further, excellent charge acceptability can be obtained, and both battery performance such as discharge characteristics and cycle characteristics can be achieved.

  The component (a) preferably comprises bisphenol A and bisphenol S. Thereby, charge acceptability, discharge characteristics, and cycle characteristics can be improved in a balanced manner.

  In the lead storage battery obtained using the bisphenol-based resin powder according to the present invention, the reason why the excellent charge / discharge characteristics are obtained as described above is that the kneadability and affinity between the bisphenol-based resin powder and the negative electrode active material are improved. Therefore, it is presumed that the reaction product generated in the electrode reaction of the lead storage battery is suppressed from being coarsened and the specific surface area of the electrode is kept high. However, the factor is not limited to this.

  The component (b) is preferably a compound represented by the following general formula (I). In this case, charge acceptability, discharge characteristics, and cycle characteristics can be further improved in a balanced manner.

［式（Ｉ）中、Ｒ_１は、アルカリ金属イオン又は水素原子を示し、ｎ１は、１〜３の整数を示す。］

[In Formula (I), R ₁ represents an alkali metal ion or a hydrogen atom, and n 1 represents an integer of 1 to 3. ]

  The weight average molecular weight of the bisphenol-based resin powder according to the present invention is preferably 10,000 to 300,000. In this case, more excellent charge / discharge characteristics can be obtained.

  The resin composition according to the present invention contains the bisphenol-based resin powder according to the present invention. Even in a battery produced using the resin composition according to the present invention, excellent cycle characteristics can be obtained.

  The pH of the resin composition according to the present invention is preferably more than 7 and 14 or less.

  The electrode according to the present invention is manufactured using the electrode active material and the bisphenol-based resin powder according to the present invention. The lead acid battery according to the present invention includes the electrode according to the present invention. With these configurations, excellent cycle characteristics can be obtained.

  The method for producing a bisphenol-based resin powder according to the present invention includes (a) a bisphenol-based compound, (b) at least one selected from the group consisting of aminonaphthalenesulfonic acid and aminonaphthalenesulfonic acid derivatives, and (c) formaldehyde and formaldehyde. A step of reacting at least one selected from the group consisting of derivatives.

  According to the method for producing a bisphenol-based resin powder according to the present invention, excellent charge / discharge characteristics can be obtained in a lead storage battery. Moreover, according to the manufacturing method of the bisphenol-type resin which concerns on this invention, the outstanding charge acceptance property is obtained and battery performance, such as a discharge characteristic and cycling characteristics, can be made compatible.

  In the method for producing a bisphenol-based resin according to the present invention, the blending amount of the component (b) is 0.5 to 1 mole with respect to 1 mole of the component (a), and the blending amount of the component (c) is the component (a). The aspect which is 2.5-3 mol in conversion of formaldehyde with respect to 1 mol is preferable. In this case, more excellent charge / discharge characteristics can be obtained.

  The method for producing a bisphenol-based resin powder according to the present invention includes (a) a bisphenol-based compound, (b) at least one selected from the group consisting of aminonaphthalenesulfonic acid and aminonaphthalenesulfonic acid derivatives, and (c) formaldehyde and formaldehyde. It is preferable to include a step of reacting at least one selected from the group consisting of derivatives and a step of producing a powder having an average particle size of 10 to 250 μm by drying a reaction product obtained in the reaction step.

  The method for producing a bisphenol-based resin powder according to the present invention can produce a spherical powder with low thermal stress and high fluidity by adopting a drying process capable of controlling the average particle size within a predetermined range. When this powder is applied as a resin for fixing an electrode active material, battery performance such as charge / discharge characteristics and cycle characteristics of the lead-acid battery can be further improved.

  The method for producing an electrode according to the present invention includes a step of producing an electrode using an electrode active material and the bisphenol-based resin obtained by the method for producing a bisphenol-based resin powder according to the present invention. The manufacturing method of the lead acid battery which concerns on this invention comprises the process of obtaining an electrode with the manufacturing method of the electrode which concerns on this invention. Also in these cases, excellent charge / discharge characteristics can be obtained.

  According to the present invention, excellent charge / discharge characteristics can be obtained in a lead-acid battery. Moreover, according to this invention, the outstanding charge acceptance property is obtained and battery performance, such as a discharge characteristic and cycling characteristics, can be made compatible. ADVANTAGE OF THE INVENTION According to this invention, the application to the lead acid battery of bisphenol-type resin powder and the application to the lead acid battery of the resin composition containing bisphenol-type resin powder can be provided.

  In particular, according to the present invention, excellent characteristics can be obtained in a lead storage battery having a negative electrode produced using an electrode active material and the bisphenol-based resin powder. ADVANTAGE OF THE INVENTION According to this invention, the application to the negative electrode of lead acid battery of bisphenol-type resin powder and the application to the negative electrode of lead acid battery of the resin composition containing bisphenol-type resin powder can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the application to the lead storage battery in the motor vehicle of the bisphenol-type resin powder and the application to the lead storage battery in the motor vehicle of the resin composition containing a bisphenol-type resin powder can be provided. Moreover, according to this invention, since it is excellent in charge acceptance, the lead storage battery which can fully be satisfied as an ISS vehicle use used in a severe environment can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application to the lead storage battery in the ISS vehicle of a bisphenol-type resin and the application to the lead storage battery in the ISS vehicle of the resin composition containing a bisphenol-type resin powder can be provided.

It is a diagram showing a measurement result of ^{1 H-NMR} spectrum of a bisphenol resin powder obtained in Example 1 of the present invention.

  Hereinafter, embodiments of the present invention will be described in detail.

<Bisphenol resin, resin composition and production method thereof>
The bisphenol-based resin constituting the resin powder according to the present embodiment includes (a) a bisphenol-based compound (hereinafter, sometimes referred to as “(a) component”), and (b) aminonaphthalenesulfonic acid and an aminonaphthalenesulfonic acid derivative. And at least one selected from the group consisting of (c) formaldehyde and a formaldehyde derivative (hereinafter, sometimes referred to as “(c) component”). And obtained by reacting. The resin composition according to the present embodiment contains the bisphenol-based resin powder according to the present embodiment. The resin composition according to the present embodiment is, for example, a composition containing bisphenol-based resin powder and a solvent (such as water), and is a resin solution that is liquid or dispersed at 25 ° C. Hereinafter, the components of the resin composition will be described.

[(A) component: bisphenol compound]
A bisphenol-based compound is a compound having two hydroxyphenyl groups. Examples of bisphenol compounds include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “bisphenol A”), bis (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl). Ethane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) butane, bis (4 -Hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and bis (4-hydroxyphenyl) sulfone (Hereinafter referred to as “bisphenol S”). These can be used individually by 1 type or in combination of 2 or more types. As the bisphenol-based compound, it is preferable to use bisphenol A and bisphenol S in combination from the viewpoint of further excellent discharge characteristics and cycle characteristics. From the viewpoint of further improving discharge characteristics and cycle characteristics, the molar ratio of bisphenol A and bisphenol is preferably 8: 2, more preferably 9: 1, and even more preferably 9.6: 0.4.

[Component (b): Aminonaphthalenesulfonic acid and aminonaphthalenesulfonic acid derivative]
Examples of the aminonaphthalenesulfonic acid include 4-amino-1-naphthalenesulfonic acid (p-form), 5-amino-1-naphthalenesulfonic acid (ana-form), 5-amino-2-naphthalenesulfonic acid (ε -Form), 6-amino-1-naphthalenesulfonic acid (ε-form), 6-amino-2-naphthalenesulfonic acid (amphi-form), 7-amino-2-naphthalenesulfonic acid, 8-amino-1- Naphthalenesulfonic acid (peri-form), 8-amino-2-naphthalenesulfonic acid (kata-form), 1-amino-3,8-naphthalenedisulfonic acid, 3-amino-2,7-naphthalenedisulfonic acid, 3- Amino-1,5-naphthalenedisulfonic acid, 6-amino-1,3-naphthalenedisulfonic acid, 7-amino-1,3-naphthalenedisulfonic acid, 7-amino -1,3,6-naphthalene trisulfonic acid, 8-amino-1,3,6-naphthalene trisulfonic acid, and the like. Examples of the aminonaphthalenesulfonic acid derivative include the monoalkali metal salt or dialkali metal salt of the naphthalenesulfonic acid described above. As the alkali metal, sodium and potassium salts are preferable.

Examples of the aminonaphthalenesulfonic acid derivative include compounds in which a part of hydrogen atoms of aminonaphthalenesulfonic acid is substituted with an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms) or the like, or a sulfo group (—SO ₃₎ of aminonaphthalenesulfonic acid. And compounds in which the hydrogen atom of H) is substituted with an alkali metal (for example, sodium or potassium). Examples of the compound in which some hydrogen atoms of aminonaphthalenesulfonic acid are substituted with an alkyl group include 5-methylamino-1-naphthalenesulfonic acid, 3-methyl-5-amino-1-naphthalenesulfonic acid, and the like. Examples of the compound in which the hydrogen atom of the sulfo group of aminonaphthalenesulfonic acid is substituted with an alkali metal include sodium 5-amino-1-naphthalenesulfonate, monosodium 3-amino-1,5-naphthalenedisulfonate, 3-amino- Disodium 1,5-naphthalenedisulfonate, sodium 7-amino-2-naphthalenesulfonate, potassium 5-amino-1-naphthalenesulfonate, monopotassium 3-amino-1,5-naphthalenedisulfonate, 3-amino- Examples include dipotassium 1,5-naphthalenedisulfonate, potassium 7-amino-2-naphthalenesulfonate, and the like.

  (B) A component can be used individually by 1 type or in combination of 2 or more types. As the component (b), 5-amino-1-naphthalenesulfonic acid is preferable from the viewpoint of further improving charge acceptability and cycle characteristics.

  The blending amount of the component (b) for obtaining the bisphenol-based resin is preferably 0.50 mol or more and 0.60 mol or more with respect to 1.00 mol of the component (a) from the viewpoint of further improving the discharge characteristics. Is more preferable, and 0.80 mol or more is still more preferable. The blending amount of the component (b) is preferably 1.30 mol or less, more preferably 1.20 mol or less with respect to 1.00 mol of the component (a), from the viewpoint that the discharge characteristics and the cycle characteristics are further improved. The amount is preferably 1.00 mol or less.

[(C) component: formaldehyde and formaldehyde derivatives]
As formaldehyde, formaldehyde in formalin (for example, an aqueous solution of 37% by mass of formaldehyde) may be used. Examples of formaldehyde derivatives include paraformaldehyde, hexamethylenetetramine, and trioxane. (C) A component can be used individually by 1 type or in combination of 2 or more types. You may use formaldehyde and a formaldehyde derivative together.

  As the component (c), a formaldehyde derivative is preferable and paraformaldehyde is more preferable from the viewpoint that excellent cycle characteristics are easily obtained. Paraformaldehyde has, for example, a structure represented by the following general formula (II).

［式（ＩＩ）中、ｎ２は２〜１００の整数を示す。］

[In formula (II), n2 represents an integer of 2 to 100. ]

  From the viewpoint of improving the reactivity of the component (b), the amount of the component (c) for obtaining the bisphenol-based resin is preferably 2 mols or more with respect to 1 mol of the component (a). 2 mol or more is more preferable, and 2.5 mol or more is still more preferable. The amount of the component (c) in terms of formaldehyde is preferably 3.5 mol or less with respect to 1 mol of the component (a) from the viewpoint of excellent solubility of the resulting bisphenol-based resin in a solvent. The following is more preferable, and 3 mol or less is still more preferable.

[solvent]
The resin composition according to this embodiment may further contain a solvent. Examples of the solvent include water (for example, ion exchange water) and an organic solvent. The solvent contained in the resin composition may be a reaction solvent used for obtaining a bisphenol-based resin.

  The resin composition according to the present embodiment may further contain a natural resin or a synthetic resin other than the bisphenol-based resin.

  The bisphenol-based resin constituting the resin powder of the present invention preferably has, for example, at least one of a structural unit represented by the following formula (III) and a structural unit represented by the following formula (IV).

［式（ＩＩＩ）中、Ｘ^３は、２価の有機基を示し、Ｒ^３１は、アルカリ金属又は水素原子を示し、Ｒ^３２は、メチロール基（−ＣＨ_２ＯＨ）を示し、Ｒ^３３及びＲ^３４は、それぞれ独立にアルカリ金属又は水素原子を示し、ｎ３１は、１〜６００の整数を示し、ｎ３２は、１〜３の整数を示し、ｎ３３は０又は１を示す。］

[In formula (III), X ³ represents a divalent organic group, R ³¹ represents an alkali metal or a hydrogen atom, R ³² represents a methylol group (—CH ₂ OH), R ³³ and R ³⁴ each independently represents an alkali metal or a hydrogen atom, n31 represents an integer of 1 to 600, n32 represents an integer of 1 to 3, and n33 represents 0 or 1. ]

［式（ＩＶ）中、Ｘ^４は、２価の有機基を示し、Ｒ^４１は、アルカリ金属又は水素原子を示し、Ｒ^４２は、メチロール基（−ＣＨ_２ＯＨ）を示し、Ｒ^４３及びＲ^４４は、それぞれ独立にアルカリ金属又は水素原子を示し、ｎ４１は、１〜６００の整数を示し、ｎ４２は、１〜３の整数を示し、ｎ４３は０又は１を示す。］

[In the formula (IV), X ⁴ represents a divalent organic group, R ⁴¹ represents an alkali metal or a hydrogen atom, R ⁴² represents a methylol group (—CH ₂ OH), R ⁴³ and R ⁴⁴ represents each independently an alkali metal or hydrogen atom, n41 represents an integer of 1 to 600, n42 represents an integer of 1 to 3, and n43 represents 0 or 1. ]

  The ratio of the structural unit represented by the formula (III) and the structural unit represented by the formula (IV) is not particularly limited, and may vary depending on synthesis conditions and the like. As the bisphenol-based resin, a resin having only one of the structural unit represented by the formula (III) and the structural unit represented by the formula (IV) may be used.

Examples of X ³ and X ⁴ include alkylidene groups (methylidene group, ethylidene group, isopropylidene group, sec-butylidene group, etc.), cycloalkylidene groups (cyclohexylidene group, etc.), phenylalkylidene groups (diphenylmethylidene group, Phenylethylidene group and the like) and sulfonyl groups. From the viewpoint of further excellent discharge characteristics and cycle characteristics, isopropylidene groups (—C (CH ₃ ) ₂ —) and sulfonyl groups (—SO ₂ —) are preferred, and isopropylidene More preferably, a group and a sulfonyl group are used in combination. X ³ and X ⁴ may be substituted with a halogen atom such as a fluorine atom. When X ³ and X ⁴ are cycloalkylidene groups, the hydrocarbon ring may be substituted with an alkyl group or the like.

Examples of the alkali metal of R ³¹ , R ³³ , R ³⁴ , R ⁴¹ , R ⁴³ and R ⁴⁴ include sodium and potassium. n31 and n41 are preferably 5 to 300 from the viewpoint of further excellent cycle characteristics and solubility in a solvent. n32 and n42 are preferably 1 or 2, and more preferably 1, from the viewpoint of improving the balance of charge acceptance, discharge characteristics, and cycle characteristics. n33 and n43 vary depending on production conditions, but 0 is preferable from the viewpoint of further excellent cycle characteristics and excellent storage stability of the bisphenol-based resin.

  The content of the bisphenol-based resin powder in the resin composition according to the present embodiment is 50 masses based on the total mass of nonvolatile components in the resin composition from the viewpoint of improving charge acceptance, discharge characteristics, and cycle characteristics in a balanced manner. % Or more is preferable, and 55 mass% or more is more preferable.

  The weight average molecular weight of the bisphenol-based resin constituting the resin powder of the present invention is 10,000 or more from the viewpoint that the cycle characteristics are easily improved by suppressing the elution of the bisphenol-based resin from the electrode into the electrolyte in the lead storage battery. Preferably, 15000 or more is more preferable, and 20000 or more is still more preferable. The weight average molecular weight of the bisphenol-based resin is preferably 300000 or less, more preferably 250,000 or less, and even more preferably 200000 or less, from the viewpoint that the cycle characteristics are easily improved by suppressing the decrease in the adsorptivity to the electrode active material. .

The weight average molecular weight of the bisphenol-based resin constituting the resin powder of the present invention can be measured, for example, by gel permeation chromatography (hereinafter referred to as “GPC”) under the following conditions. (GPC conditions)
Apparatus: High performance liquid chromatograph LC-2200 Plus (manufactured by JASCO Corporation)
Pump: PU-2080
Differential refractometer: RI-2031
Detector: UV-visible spectrophotometer UV-2075 (λ: 254 nm)
Column oven: CO-2065
Column: TSKgel SuperAW (4000), TSKgel SuperAW (3000), TSKgel SuperAW (2500) (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Eluent: methanol solution containing LiBr (10 mM) and triethylamine (200 mM) Flow rate: 0.6 mL / min Molecular weight standard sample: Polyethylene glycol (molecular weight: 1.10 × 10 ⁶ , 5.80 × 10 ⁵ , 2.55 × 10 ⁵ , 1.46 × 10 ⁵ , 1.01 × 10 ⁵ , 4.49 × 10 ⁴ , 2.70 × 10 ⁴ , 2.10 × 10 ⁴ ; manufactured by Tosoh Corporation), diethylene glycol (molecular weight: 1 .06 × 10 ² ; manufactured by Kishida Chemical Co., Ltd.), dibutylhydroxytoluene (molecular weight: 2.20 × 10 ² ; manufactured by Kishida Chemical Co., Ltd.)

  The content of the unreacted component (residual component) in the resin composition containing the bisphenol-based resin powder according to the present embodiment is 1% by mass based on the total mass of the resin composition from the viewpoint of further improving cycle characteristics. The following is preferable, 0.9 mass% or less is more preferable, and 0.8 mass% or less is still more preferable. The content of unreacted components can be reduced by, for example, drying the resin composition. The content of unreacted components can be measured, for example, by gas chromatography.

  The water content in the composition containing the bisphenol-based resin powder according to the present embodiment is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of excellent quality control and operability. % Or more is more preferable. From the same viewpoint, the water content is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less. The amount of water can be measured, for example, by Karl Fischer titration.

  The manufacturing method of the bisphenol-type resin powder which concerns on this embodiment is equipped with the resin manufacturing process which makes (a) component, (b) component, and (c) component react, and obtains a bisphenol-type resin. The composition containing the bisphenol-based resin powder according to the present embodiment may be a composition obtained in the resin powder manufacturing process, and is obtained by mixing the bisphenol-based resin powder and other components after the resin powder manufacturing process. Composition may be used.

  The bisphenol-based resin can be obtained, for example, by reacting the component (a), the component (b), and the component (c) in a reaction solvent. The reaction solvent is preferably water (for example, ion exchange water). In order to promote the reaction, an organic solvent, a catalyst, an additive, or the like may be used.

  In the resin production process, from the viewpoint of further improving cycle characteristics, the blending amount of component (b) is 0.5 to 1.5 moles per mole of component (a), and blending of component (c) The aspect whose amount is 2.5-3 mol in conversion of formaldehyde with respect to 1 mol of (a) component is preferable. (B) The preferable compounding quantity of a component and (c) component is the range mentioned above about each of the compounding quantity of (b) component and (c) component.

  The bisphenol-based resin constituting the resin powder according to the present embodiment is based on basic conditions (alkaline conditions) with the components (a), (b), and (c) from the viewpoint that a sufficient amount of bisphenol-based resin can be easily obtained. It is preferable to obtain it by making it react. In order to adjust to basic conditions, you may use a basic compound. Examples of the basic compound include sodium hydroxide, potassium hydroxide, and sodium carbonate. A basic compound can be used individually by 1 type or in combination of 2 or more types. Among the basic compounds, sodium hydroxide and potassium hydroxide are preferable from the viewpoint of excellent reactivity.

  When the reaction solution containing the component (a), the component (b) and the component (c) is neutral (pH = 7) at the start of the reaction, the formation reaction of the bisphenol-based resin may not easily proceed. If the solution is acidic (pH <7), side reactions may proceed. Therefore, the pH of the reaction solution at the start of the reaction is preferably alkaline (exceeding 7) from the viewpoint of suppressing the side reaction from proceeding while the bisphenol-based resin formation reaction proceeds, and is 7.1 or more Is more preferable, 8 or more is further preferable, and 8.5 or more is particularly preferable. The pH of the reaction solution is preferably 14 or less, more preferably 13 or less, and still more preferably 12 or less, from the viewpoint of suppressing the hydrolysis of the group derived from the component (b) of the bisphenol-based resin. The pH of the reaction solution can be measured by, for example, Twin pH manufactured by AS ONE Corporation. The pH is defined as the pH at 25 ° C.

  Since it is easy to adjust the pH as described above, it is preferable to blend a strongly basic compound. The compounding amount of the strongly basic compound is preferably 1.01 mol or more, more preferably 1.02 mol or more, and further preferably 1.05 mol or more with respect to 1 mol of the sulfo group contained in the component (b). From the same viewpoint, the compounding amount of the strongly basic compound is preferably 1.5 mol or less, more preferably 1.3 mol or less, more preferably 1.2 mol with respect to 1 mol of the sulfo group contained in the component (b). The following is more preferable. Examples of the strongly basic compound include sodium hydroxide and potassium hydroxide.

  In this embodiment, the reaction product (reaction solution) obtained by the method for producing a bisphenol-based resin may be used as it is for the production of an electrode to be described later, but the bisphenol-based resin powder obtained by drying the reaction product is used as a solvent ( It is preferably dissolved in water or the like and used for the production of the electrode described later.

  Examples of the drying method include freeze drying, vacuum drying, spray drying, and heat drying. Heat drying and spray drying are preferable for the purpose of treating bisphenol resins quickly and in large quantities, and spray drying is further used for the purpose of reducing heat stress and maintaining the shape of the bisphenol resin after drying in a highly fluid spherical shape. preferable.

  The average particle size of the bisphenol-based resin powder obtained by the drying method such as spray drying is preferably 1-1000 μm. When it becomes 1000 μm or more, solubility in water decreases. If it is 1 μm or less, it will be scattered during handling, and it will be easily charged and adhere to the surroundings will increase. In addition, the smaller the average particle size, the easier it is to generate lumps (lumps) when dissolved in water, and the handleability becomes significantly worse. From these viewpoints, the particle size of the bisphenol-based resin is preferably 1 to 1000 μm, more preferably 5 to 500 μm, and further preferably 10 to 250 μm from the viewpoint of handleability when kneading with lead particles as a powder. preferable.

  The average particle size of the bisphenol resin powder is, for example, using a laser diffraction scattering system flow distribution measuring device, and uniformly dispersing the resin powder sample in an aqueous solution to which a surfactant such as polyoxyethylene cumylphenyl ether is added as a dispersion medium Can be measured. Specifically, the cumulative curve is obtained by setting the total volume of fine particles obtained by analyzing the scattered light of the laser by the microtrack method to 100%, and the particle size at which the cumulative curve from the small particle size side becomes 50% ( The median diameter, d50) is defined as the average particle diameter of the bisphenol resin powder.

  The pH of the resin composition (for example, a resin solution that is liquid at 25 ° C.) is excellent in solubility in a solvent (water, etc.) of a bisphenol-based resin in the battery manufacturing process described later, and has an electrode active material (lead, lead oxide, etc.). From the viewpoint of excellent wettability of the resin composition to), it is preferably alkaline (greater than 7), more preferably 7.1 or more. The pH of the resin composition is preferably 7.5 or more from the viewpoint of further excellent solubility of the bisphenol-based resin in a solvent (such as water). The pH of the resin composition is preferably 8 or more from the viewpoint of further improving the wettability of the resin composition to an electrode active material (lead, lead oxide, etc.). The pH of the resin composition is preferably 14 or less, more preferably 13.5 or less, and even more preferably 13 or less, from the viewpoint of reducing hydrolysis of the group derived from the component (b) of the bisphenol-based resin. The pH of the resin composition is preferably 12 or less from the viewpoint of further improving the wettability of the resin composition to an electrode active material (lead, lead oxide, etc.). In particular, the pH when the bisphenol-based resin is adjusted to a 5% by mass aqueous solution (for example, an aqueous solution containing ion-exchanged water) is preferably in the above range. Moreover, when using the composition obtained in a resin manufacturing process as a resin composition, it is preferable that pH of a resin composition is the said range. The pH of the resin composition can be measured by, for example, Twin pH manufactured by AS ONE Corporation. The pH is defined as the pH at 25 ° C. The pH of the resin composition can be adjusted using, for example, a 10% by mass aqueous sodium hydroxide solution.

  The synthesis reaction of the bisphenol-based resin is sufficient if the (a) component, the (b) component, and the (c) component react to obtain a bisphenol-based resin. For example, the (a) component, (b) component, and (c) The components may be reacted at the same time, or the remaining one component may be reacted after reacting two of the components (a), (b) and (c).

  The synthesis reaction of the bisphenol-based resin is preferably performed in two steps as follows. In the first stage reaction, for example, the component (b), a solvent (water, etc.) and a basic compound (for example, a strong basic compound) are charged and stirred, and the hydrogen atom of the sulfo group in the component (b) is alkali metal. To obtain an alkali metal salt of the component (b). Thereby, it becomes easy to suppress a side reaction in the below-mentioned condensation reaction. The temperature of the reaction system is preferably 0 ° C. or higher, more preferably 25 ° C. or higher, from the viewpoint of excellent solubility of the component (b) in a solvent (such as water). The temperature of the reaction system is preferably 80 ° C. or less, more preferably 70 ° C. or less, and still more preferably 60 ° C. or less from the viewpoint of suppressing side reactions. The reaction time is, for example, 5 to 30 minutes.

  In the second stage reaction, for example, the component (c) is added to the reaction product obtained in the first stage, stirred for 5 to 30 minutes until the mixture becomes a transparent homogeneous system, and then the component (a) is added to the mixture. In addition, a bisphenol-based resin is obtained by a condensation reaction. The temperature of the reaction system is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, and still more preferably 95 ° C. or higher, from the viewpoint of excellent reactivity of the components (a), (b) and (c). The temperature of the reaction system is preferably 120 ° C. or lower, more preferably 115 ° C. or lower, from the viewpoint of suppressing evaporation of the reaction solvent (for example, water). The reaction time is, for example, 1 to 10 hours.

  The reaction product thus obtained is dried to remove the solvent (water and the like), the unreacted component (c), and the like, thereby obtaining a bisphenol-based resin. The drying method is not particularly limited, but a method in which the temperature of the bisphenol-based resin is 100 ° C. or lower is preferable from the viewpoint of preventing the self-curing reaction of the bisphenol-based resin and keeping the particle size distribution uniform. Examples of the drying method include reduced-pressure drying, freeze drying, and spray dry drying. In the present invention, spray dry drying is preferable.

<Electrode, lead acid battery, and manufacturing method thereof>
The electrode according to the present embodiment is manufactured using the electrode active material and the bisphenol-based resin powder according to the present embodiment or the resin composition containing the bisphenol-based resin powder. The manufacturing method of the electrode which concerns on this embodiment is equipped with the process of manufacturing an electrode using the bisphenol-type resin powder obtained by the manufacturing method of the bisphenol-type resin which concerns on this embodiment. The electrode includes, for example, an electrode layer containing an electrode active material and a current collector that supports the electrode layer. The electrode is, for example, a negative electrode (a negative electrode plate or the like) for a lead storage battery.

  The lead storage battery according to the present embodiment includes the electrode according to the present embodiment. Examples of the lead storage battery according to this embodiment include a liquid lead storage battery and a sealed lead storage battery, and a liquid lead storage battery is preferable. The method for manufacturing a lead storage battery according to the present embodiment includes, for example, an electrode manufacturing process for obtaining an electrode by the electrode manufacturing method according to the present embodiment, and an assembly process for obtaining a lead storage battery by assembling components including the electrode. Yes.

  In the electrode manufacturing process, for example, after filling an electrode paste into a current collector (for example, current collector grid), aging and drying are performed to obtain an unformed electrode. The electrode paste contains, for example, an electrode active material and a bisphenol-based resin powder, and may further contain other predetermined additives. When the electrode is a negative electrode, the negative electrode active material is preferably lead powder (PbO). Examples of the additive include barium sulfate, a carbon material, and reinforcing short fibers (acrylic fiber, polyethylene fiber, polypropylene fiber, polyethylene terephthalate fiber, carbon fiber, etc.). Examples of the carbon material include carbon black and graphite. Examples of carbon black include furnace black, channel black, acetylene black, thermal black, and ketjen black.

  When the electrode according to this embodiment is a negative electrode, the negative electrode paste can be obtained, for example, by the following method. First, a mixture is obtained by adding bisphenol-based resin powder or a resin composition containing the bisphenol-based resin powder to lead powder and, if necessary, an additive and mixing. Next, negative sulfuric acid paste is obtained by adding dilute sulfuric acid and a solvent (such as water) to this mixture and kneading.

  In the negative electrode paste, when barium sulfate is used, the compounding amount of barium sulfate is preferably 0.01 to 1% by mass based on the total mass of the negative electrode active material. Moreover, when using a carbon material, the compounding quantity of a carbon material has preferable 0.2-1.4 mass% on the basis of the total mass of a negative electrode active material. The blending amount of the bisphenol-based resin powder according to the present embodiment or the resin composition containing the bisphenol-based resin powder is 0.01 to 2% by mass in terms of resin solid content based on the total mass of the negative electrode active material. Preferably, 0.05-1 mass% is more preferable, and 0.1-0.5 mass% is still more preferable.

  Examples of the material of the current collector include a lead-calcium-tin alloy, a lead-calcium alloy, and alloys obtained by adding a small amount of arsenic, selenium, silver, bismuth, or the like to these.

  The aging conditions are preferably 15 to 60 hours in an atmosphere at a temperature of 35 to 85 ° C. and a humidity of 50 to 98 RH%. Drying conditions are preferably 15 to 30 hours at a temperature of 45 to 80 ° C.

When the electrode which concerns on this embodiment is a negative electrode, the positive electrode (positive electrode plate etc.) for lead acid batteries can be obtained by the following method, for example. First, after adding a reinforcing short fiber to lead powder (PbO) which is an electrode active material, water and dilute sulfuric acid are added. This is kneaded to produce a positive electrode paste. In producing the positive electrode paste, red lead (Pb ₃ O ₄ ) may be added. After filling this positive electrode paste into a current collector (for example, current collector grid), aging and drying are performed to obtain an unformed positive electrode. In the positive electrode paste, the blending amount of the reinforcing short fibers is preferably 0.005 to 0.3% by mass based on the total mass of the lead powder. The type of current collector, aging conditions, and drying conditions are almost the same as in the case of the negative electrode.

  In the assembly process, for example, the negative electrode and the positive electrode produced as described above are alternately stacked via separators, and electrode plates having the same polarity are connected with a strap to obtain a plate group. This electrode group is arranged in a battery case to produce an unformed battery. Next, dilute sulfuric acid is added to the non-chemical cell to perform chemical conversion treatment. Subsequently, after removing the diluted sulfuric acid once, a lead storage battery is obtained by adding an electrolytic solution (sulfuric acid or the like). The specific gravity (converted to 20 ° C.) of sulfuric acid is preferably 1.25 to 1.35.

  Examples of the material of the separator include polyethylene and glass fiber. The chemical conversion conditions and the specific gravity of sulfuric acid can be adjusted according to the properties of the electrode active material. The chemical conversion treatment is not limited to being performed in the assembly process, and may be performed in the electrode manufacturing process.

  Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to the following examples.

<Preparation of negative electrode plate>
[Example 1]
After adding 39.4 parts by mass of 25 wt% aqueous sodium hydroxide and 137.8 parts by mass of ion-exchanged water to a 500 mL separable flask equipped with a Dimroth, mechanical stirrer, and thermometer, the mixture was stirred at 150 rpm for 5 minutes to obtain sodium hydroxide. An aqueous solution was prepared. A uniform aqueous solution was obtained by adding 22.3 parts by mass of 5-amino 1-naphthalenesulfonic acid to this aqueous sodium hydroxide solution and stirring at 25 ° C. for 10 minutes. After adding 9.6 mass parts (formaldehyde conversion) of paraformaldehyde to this aqueous solution, it stirred for 5 minutes and dissolved paraformaldehyde, and obtained uniform aqueous solution. After adding 22.8 parts by mass of bisphenol A to this aqueous solution, the mixture was heated using an oil bath set at 115 ° C. and stirred for 5 hours after the temperature in the flask reached 95 ° C. The obtained reaction solution was dried by a spray drying method to produce a resin powder.
The spray drying conditions are shown below.
Manufacturer model number: TR160 (Drying room diameter φ1600mm) (Pris made)
System flow: Open cycle system Spraying method: Atomizer disk method Product collection method: Two-point collection method (under the main body, under the cyclone)
Sample flow rate: 1.8 kg / h
Inlet temperature: 180 ° C
Outlet temperature: 110 ℃
Atomizer speed: 4,000 to 10,000 rpm
Hot air flow rate: 3 m ³ / min

The ¹ H-NMR spectrum of the bisphenol-based resin powder obtained in Example 1 was measured under the following conditions. The measurement result of ¹ H-NMR spectrum is shown in FIG.
Device: AVANCE300 (manufactured by Nippon Bruker Co., Ltd.)
Heavy solvent: DMSO-d ₆
From the ¹ H-NMR spectrum of FIG. 1, the bisphenol resin powder of Example 1 has at least one of the structural unit represented by the above formula (III) and the structural unit represented by the above formula (IV). confirmed.

The weight average molecular weight of the bisphenol-based resin powder obtained in Example 1 was measured by GPC under the following conditions. The weight average molecular weight measured using GPC was 90000.
Apparatus: High performance liquid chromatograph LC-2200 Plus (manufactured by JASCO Corporation)
Pump: PU-2080
Differential refractometer: RI-2031
Detector: UV-visible spectrophotometer UV-2075 (λ: 254 nm)
Column oven: CO-2065
Column: TSKgel SuperAW (5000), TSKgel SuperAW (4000), TSKgel SuperAW (3000), TSKgel SuperAW (2500) (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Eluent: methanol solution containing LiBr (10 mM) and triethylamine (200 mM) Flow rate: 0.6 mL / min Molecular weight standard sample: Polyethylene glycol (molecular weight: 1.10 × 10 ⁶ , 5.80 × 10 ⁵ , 2.55 × 10 ⁵ , 1.46 × 10 ⁵ , 1.01 × 10 ⁵ , 4.49 × 10 ⁴ , 2.70 × 10 ⁴ , 2.10 × 10 ⁴ ; manufactured by Tosoh Corporation), diethylene glycol (molecular weight: 1 .06 × 10 ² ; manufactured by Kishida Chemical Co., Ltd.), dibutylhydroxytoluene (molecular weight: 2.20 × 10 ² ; manufactured by Kishida Chemical Co., Ltd.)

The pH of the aqueous solution containing 5% by mass of the bisphenol-based resin powder obtained in Example 1 was measured under the measurement conditions described above.
Testing machine: Twin pH (manufactured by ASONE Corporation)
Calibration solution: pH 6.86 (25 ° C.), pH 4.01 (25 ° C.)
Measurement temperature: 25 ° C
Measurement procedure: Two-point calibration was performed using a calibration solution. After washing the sensor part of the testing machine, the measurement solution was sucked with a dropper, and 0.1 to 0.3 mL was dropped onto the sensor part. The pH at the end of measurement on the screen was taken as the measured value.

  The average particle diameter (μm) of the bisphenol-based resin powder obtained in Example 1 is 0.5% by mass of polyoxyethylene cumylphenyl ether as a dispersion medium using a laser diffraction scattering type flow distribution measuring device manufactured by Nikkiso. A resin powder sample was uniformly dispersed in an aqueous solution and measured to obtain the median diameter (d50).

  Based on the total mass of the lead powder, 0.2% by mass of bisphenol resin powder, 0.2% by mass of furnace black, and 1.0% by mass of barium sulfate were added to the lead powder and then dry mixed. Next, the mixture was kneaded while adding dilute sulfuric acid (specific gravity 1.26 (converted at 20 ° C.)) and water to prepare a negative electrode paste. The negative electrode paste was filled into an expanded current collector (lead-calcium-tin alloy) having a thickness of 0.6 mm to produce a negative electrode plate. The negative electrode plate was aged for 18 hours in an atmosphere of a temperature of 50 ° C. and a humidity of 95% according to a normal method, and then dried in an atmosphere of a temperature of 50 ° C. to obtain an unformed negative electrode plate.

[Examples 2-3]
A negative electrode plate was obtained in the same manner as in Example 1 except that the average particle size of the bisphenol-based resin powder was changed by adjusting the drying conditions by the spray drying method. Further, in the same manner as in Example 1, the weight average molecular weight of the bisphenol resin, the pH of the aqueous solution containing 5% by mass of the bisphenol resin, and the average particle diameter were measured. In Table 1, the amount of paraformaldehyde is a formaldehyde equivalent.

[Examples 4 to 6]
Example except that the components for obtaining the bisphenol-based resin were changed to the components shown in Table 1 below, and the average particle size of the bisphenol-based resin powder was changed by adjusting the drying conditions by the spray drying method. A negative electrode plate was obtained in the same manner as in Example 1. Further, in the same manner as in Example 1, the weight average molecular weight of the bisphenol resin, the pH of the aqueous solution containing 5% by mass of the bisphenol resin, and the average particle diameter were measured. In Table 1, the amount of paraformaldehyde is a formaldehyde equivalent.

[Comparative Example 1]
A negative electrode plate was obtained by the same method as in Example 1 except that the components for obtaining the bisphenol-based resin were changed to the components shown in Table 1 and the drying step by the spray drying method was not performed. Further, in the same manner as in Example 1, the weight average molecular weight of the bisphenol resin, the pH of the aqueous solution containing 5% by mass of the bisphenol resin, and the average particle diameter were measured. In Table 1, the blending amount of 37 mass% formalin is a blending amount in terms of formaldehyde.

<Preparation of positive electrode plate>
After adding 0.01% by mass of cut fiber (polyethylene fiber) to the lead powder based on the total mass of the lead powder, dry mixing was performed. Next, dilute sulfuric acid (specific gravity 1.26 (converted at 20 ° C.)) and water were added and kneaded to prepare a positive electrode paste. A positive electrode current collector (lead-calcium-tin alloy) made of a cast grid is filled with a positive electrode paste and left to mature for 18 hours in an atmosphere at a temperature of 50 ° C. and a humidity of 95%, and then an atmosphere at a temperature of 50 ° C. It dried below and obtained the unchemically formed positive electrode plate.

<Battery assembly>
After laminating 6 unformed negative plates and 5 unformed positive plates through polyethylene separators so that unformed negative plates and unformed positive plates are alternately laminated, the same polarity electrode plate The electrode plates were made by connecting them with a strap. The electrode plate group was inserted into the battery case to assemble a 2V single cell battery. After dilute sulfuric acid (specific gravity 1.28 (converted at 20 ° C.)) was poured into this battery, it was formed in a 50 ° C. water bath under an electric current of 1.0 A for 15 hours. And after discharging | emitting dilute sulfuric acid, the dilute sulfuric acid of specific gravity 1.28 (20 degreeC conversion) was inject | poured again and the lead acid battery was obtained.

<Evaluation of battery characteristics>
About said 2V single cell battery, charge acceptance, discharge characteristics, and cycling characteristics were measured as follows. The measurement results of charge acceptance, discharge characteristics, and cycle characteristics of Comparative Example 1 were set to 100, and each characteristic was relatively evaluated. The results are shown in Table 1.

(Charge acceptance)
5 seconds after the state of charge of the battery has reached 90%, that is, 10% of the battery capacity is discharged from the fully charged state and charged at a constant voltage of 2.33 V. The current value of was measured. The larger the current value after 5 seconds, the better the initial charge acceptance.

(Discharge characteristics)
As discharge characteristics, a constant current discharge was performed at −15 ° C. at 5 C, and the discharge duration until the battery voltage reached 1.0 V was measured. The longer the discharge duration, the better the battery. The C means “discharge current value (A) / battery capacity (Ah)”.

(Cycle characteristics)
The cycle characteristics were evaluated by a method according to a Japanese Industrial Standard light load life test (JIS D 5301). The larger the number of cycles, the higher the durability.

(Evaluation of storage stability)
Storage stability was evaluated by the following procedure. After 30 mL of the resin solution was put into a φ30 × 65 glass container, it was stored at 40 ° C. using a thermostatic bath. And the said 2V single cell battery was produced using this resin solution every month, and the said battery characteristic was measured. As battery characteristics, charge acceptability, discharge characteristics, and cycle characteristics were evaluated in the same manner as described above. The point at which the charge acceptability decreased by 2%, the discharge characteristics decreased by 2%, or the cycle characteristics decreased by 10% compared to before storage was evaluated as the storage limit. The results are shown in Table 1 below.

  In the examples, it can be confirmed that by using bisphenol-based resin powder and further controlling the average particle diameter, the cycle characteristics are greatly improved as compared with the comparative example, and the storage stability is also excellent. In addition, the charge acceptability and the discharge characteristics remain almost the same as those in Comparative Example 1, and it can be confirmed that the performance as, for example, an ISS vehicle can be sufficiently satisfied. Thus, it can be confirmed that the examples are compatible with excellent charge acceptability, discharge characteristics, and cycle characteristics.

  ADVANTAGE OF THE INVENTION According to this invention, the bisphenol-type resin powder which can acquire the cycling characteristics outstanding in the lead acid battery, and its manufacturing method can be provided. Moreover, according to this invention, the resin composition containing the said bisphenol-type resin powder can be provided. Furthermore, according to this invention, the electrode manufactured using an electrode active material and the said bisphenol-type resin, lead acid battery, and these manufacturing methods can be provided.

Claims (13)

  A reaction between (a) a bisphenol-based compound, (b) at least one selected from the group consisting of aminonaphthalenesulfonic acid and aminonaphthalenesulfonic acid derivatives, and (c) at least one selected from the group consisting of formaldehyde and formaldehyde derivatives. A bisphenol-based resin powder obtained by processing.   The bisphenol-based resin powder according to claim 1, wherein the average particle size is 10 to 250 μm.   The bisphenol-based resin powder according to claim 1 or 2, wherein the component (a) comprises bisphenol A and bisphenol S.   The bisphenol-type resin powder as described in any one of Claims 1-3 whose weight average molecular weights are 10,000-300000.   The resin composition containing the bisphenol-type resin powder as described in any one of Claims 1-4.   The resin composition according to claim 5, wherein the pH is more than 7 and 14 or less.   The electrode which has an electrode active material and the bisphenol-type resin powder as described in any one of Claims 1-4.   A lead acid battery comprising the electrode according to claim 7.   (A) reacting a bisphenol-based compound with (b) at least one selected from the group consisting of aminonaphthalenesulfonic acid and aminonaphthalenesulfonic acid derivatives, and (c) at least one selected from the group consisting of formaldehyde and formaldehyde derivatives. The manufacturing method of the bisphenol-type resin powder provided with the process to make.   The blending amount of the component (b) is 0.5 to 1 mole with respect to 1 mole of the component (a), and the blending amount of the component (c) is in terms of formaldehyde with respect to 1 mole of the component (a). The manufacturing method of the bisphenol-type resin powder of Claim 9 which is 2.5-3 mol.   (A) the bisphenol compound, (b) at least one selected from the group consisting of aminonaphthalenesulfonic acid and aminonaphthalenesulfonic acid derivatives, and (c) at least one selected from the group consisting of formaldehyde and formaldehyde derivatives, The method for producing a bisphenol-based resin powder according to claim 9 or 10, comprising a step of reacting and a step of drying a reaction product obtained in the reaction step to produce a powder having an average particle size of 10 to 250 µm.   The manufacturing method of an electrode provided with the process of manufacturing an electrode using an electrode active material and the bisphenol-type resin powder obtained by the manufacturing method of the bisphenol-type resin powder as described in any one of Claims 9-11. .   The manufacturing method of a lead acid battery provided with the process of obtaining an electrode with the manufacturing method of the electrode of Claim 12.

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